Photographic developer



Patent ed June 193$ "UNITED s'r res PATENT. OFFICE 2,188,166 I PHOTOGRAPHIODEVELOPER v, Gustav Wilmanns, Woll'en, Bitterfeld, and Wilhelm Schneider and Bruno Wendt, Dessau, Anhalt, Germany, assignors, by mesne assignments, to Agfa Ansco Corporation, Bingham ton, N. Y., a. corporation of Delaware 1 I No Drawing. Application May 20,1937. Serial No; 143,724. In Germany May. 26, 1936 5 Claims. (Cl. 95'-88) Our present invention relates to photographic developers and more particularly to developers for development in colors.

One of-its objects is to provide new photographic developers of the para-phenylenediamine series. Further objects will be seen-from the detailed specification following hereafter.

Para-phenylenediamine is a known developer for silver halide emulsions. It is also known that wthe substitution products of developers of this class form, with suitable dyestuif "components, color pictures in the development. Substances suitable are described in UJS. Patent, 1 ,'102,028, dated June 30, 1914. Hitherto only'thederivatives of para-phenylenediamine whi'cii'are alkylated at the nitrogen atom have been used as color developers. All these bodies and especially the most suitable of them are, however, of only limited solubility in water or in a sodium carbonate solution. This fact is a drawback in that the developer is removed only withd'ifliculty by washing after the development, so that in sub- "sequent ly bleaching the silver picture with an oxidizing agent such as potassiumferricyanide undesired color is apt to be developed, particularly when suitable components are present;

Moreover, these substances are freely absorbed by the skin and give rise to malignant eczema and like troubles. All these disadvantages would be considerably ameliorated if the solubility of the compounds could be increased. It has been found that the introduction of 'carboxylic groups or sulfonic groups for increasing'the solubility is not satisfactory in this caseifl'the group enters the nucleus of the para-phenylenediamine, because then. the developing power is at the least strongly diminished.

This invention is based on the observation that valuable developing agents, particularly suitable for development in colors, may be obtained by introducing a sulfonlc or carboxylic group into a positive radical 'attachedto the nitrogen, so as to produce for example, paraamino-N-methyl-aniline-omega-sulfonic a c i d, para-amino-N-ethylaniline-omega-sulfonic acid. 4-amino-N-benzyl-aniline-4'-sulfonic acid, and so on. A formula for the developers of this invention is the following:

R Y R =alkylene arylene 1 ii=coonfsoan the para-phenylenediamine is unsubstituted or contains a further substituent in the free orthoor meta-position, a radical which contains several oxy-groups. It has already been proposed in U. S. Patent 2,108,243 dated February 15, 1938 to introduce hydroxyethyl-groups in the paraphenylenediamine. It has been shown, however,

that the solubility is not-sumcient to render the base easily soluble in water. The solubility is attained, however, if the paraphenylenediamine is caused to react with ethylene-oxide, for instance with 3 --to 5mol-ethylene-oxide. This ex- R X R=any positive groups, for instance hydrogen, alkyl aryl or hydroxyalkyl Nv X=[CH.OH1.O],.-CHMJHLOH n=a whole number These developers are well suited for black and white and also for color development, and their superior solubility and physiological harmlessness distinguish them from known phenylene= diamines. f

The two groups of' developers may be. combined in accordance with the following formula:

The following examples illustrate the invention: (1) 1 mol methylphenylamino-benzyl-2-propicnic acid is coupled with 1 mol of diazotized sulfanilic acid in the usual manner. The dye is precipitated and is filtered off and split by reducing with tin and hydrochloric acid. The tin is precipitated from the solution of the double-salt by means of sulfuretted hydrogen and the resulting developing agent is obtained by evaporating (2)1 mol"'of p-sulfobenzylaniiine is. coupled with l'molof diazotized sulfa'nilic acid, the dye is isolated and split in the same manner as disclosed in Example 1 with tin and hydrochloric acid. The hydrochloride of p-sulfobenzylamino-4-aniline is obtained from the tin double-salt and corresponds to the following formula:

W t rm Nm (3) 1 mol of di-(p -sulfobenzyD-aniline is coupled with 1 mol of diazotized sulfanilic acid and further treated in a manner analogous to that of Example 1. Di'-(p-su1fobenzyl)-aminoanilinehydrochloride which has the following formula:

(5) 1 mol of a condensation product obtained from 1 mol nitromethyl-m-toluidine and 2 mols ethyleneoxide yields after reduction with tin and hydrochloric acid. a product of the following formula:

CHr-N-JJHpOHnOJIHaCHLOH NHLHCI (6) 1 mol of a condensation product produced by the known method from 1 mol of ethylaniline and 2 mols of ethyleneoxide yields if treated according to the method of Example 1 a developer of the following formula:

NHI-HCI (7) 1 mol of the condensation product from 1 mol monoethyl-m-toluidine and 2 mols ethyleneoxide is treated in the same manner as described in Example 1. A compound of the following formula is obtained:

4 'OsHr-N-CHaCHaQCHaOHaOH I Name! What we claim is: g 1. A photographic developer containing a p-phenylenediamine having attached to one of the nitrogen atoms the radicle (CH2.CH2.O) a.CH:.CHs.OH,

wherein n is a whole number.

2. A photographic developer containing a p-phenylenediamine having attached to one of the nitrogen atoms the radicle (CHz.CH:.0) .CH:.CH:.OH,

wherein n is a whole number and a member selected from the group consisting of hydrogen.

alkyl, aryl and aralkyl.

3. A photographic developer containing a p-phenylenediamine corresponding with the following formula cmt-N-cmcmocm.0n,.o .cm.cm.on

NHI-HCI 4. A photographic developer containing a p-phenyienediamine corresponding with the following formula CHEN-Clix.0H|.0.CH1.CH1.0H

NHsHCl 5. A photographic developer containing a p-phenylenediamine corresponding with the following formula NHaHCl GUSTAV WILMANNS. 

